Process for breaking petroleum emulsions



Patented Dec. 31, 1935 PROCESS FOR BREAKING PETROLEUM v a EMULSIONS 'Melvin .De Groote, St. Louis, Bernhard Keiser,

, Webster Groves, and Arthur F. Wlrtel, Richniond Heights, Mo., assi'gnors, to Tretolite Companmuzlvebster Groves, Mo., a corporation of 1 lie Drawing.

This invention relates to the treatment of emulsions of mineral oil and water, such as petroleum emulsions, for the purpose of separating :the oil from thewater. a I

Petroleum emulsions are of the ,water-in-oil type, and comprise flne droplets of naturallyoccurring waters or brines, dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. They are obtained from producing wells and from the bottom of oil storage tanks, and are commonly referredto as cut oil", roily'oil, emul- 1 sided oil" and bottom settlings.

v The object .of our invention is to provide a novel and inexpensive process for separating emulsions of the character referred to' into their component-parts of oil and water or brine. I Briefly described, our process consists in subjecting a petroleum emulsion of the water-in-oil type to the action of a treating agent or demulsifying agent of the kind hereinafter described, I

thereby causing the emulsion to break down and separateinto its component parts of oil and water orbrine, when theemulsion is permitted to remain in "a quiescent state after treatment, or is subjected to other equivalent separatory procedures. s i I Thetreating agent usedin our-process consists of a .poly keto fatty acid body or' -bodies. "It is well known that certain fatty acids '=or fatty bodies can ,be subjected to treatment '50 85.110 yield keto -fatty acids' that is, fatty acids in which 'a 'ketonic group a carbonyl group) 'is present. One example is theconversion of ricinoleic acid into ketohydroxystearicIacid. Such, I II I, II I I ting'sulfonic acid, such as approximately ketohydroxystearic acid can be reacted "with other acids, particularly other hydroxy acids, to give polymerized acids, or more correctly, poly keto acids which hayeythe same analogy to keto acids as triricinoleic acid or diricinoleic acid has to ricinoleic acid. I I

Poly keto fatty acids can be obtained by the cautious oxidation of unsaturated, hydroxylated, fatty bodies of various kinds. In the-co pending application for, patent of De Groote and Keiser, Serial No. 760,025, died December 31, 1934, there is described the=prcdiiction of unsaturated, hydroxylated, iatt -mate'iial's obtainedby the oxidation ofrelatiye yhighly unsaturated, nonhydroxylatedjinaterial, such as semi-drying oils, drying oils, marine oils, or their fattyacids or mixtures thereof,- The raw material, prior to oxidation, is characterized by a relatively high I n s x ,However, oxidationnot only takes place at the hydroxyl position, but at theethylene link-.

'iodine number, such asl20-to 180 or'l90.

a In the production of poly ketofatty'acids, or

as disclosed in our. aforementioned cc-p'ending an alcoho1,,.and in'fact, a se on ary; alcohol. n

is furthermore w n known'that litipm acids are produced by the cautious oxidation of marox'y.

jraceinic acid; Insaid reaction the CH(OH)" group be indicated by'thefollowingformulalw I Application December v I Serial No. 160,032 12 Claims, (Cristi- 4) their or, ems, by pressure oxidation at relatively low temperatures,one mayemploy any suitable unsaturated,,hydroxylated fatty mate-- rial, such as castor oil, ricin'oleic acid. diricinoleic a acid, material-of the kind described in the afore- 5 mentioned application for patent of DeJGroote and Keiser, r any other suitable material; In ourco-pendin'g application for patent Serial No.

750,031, filed December 31, .1934, -we'ha've describedthepoly keto fatty a'cidsand their salts and. esters Iasnew 'ccmpositions of matter, and I also a, new method for producing the same, i'.,e.,

tures, such as 135 C. or less. I v I I I a It is suflicient for the present purpose to state pressure oxidation at relatively low, temperathat the process ofour'saidapplication for patent produces materials hishin poly keto fatty f acids, which have, thefsame characteristics, as poly keto fattyacids derived by esterifying or condensing a keto :fatty acid, such .as keto hyo droxy fattyacid-wi th ricinoleic acid or diricinoleic I acid or 'oleicacidor triricinoiein; I I t I I Briefly described, the method of producing I such poly ketofatty acids by pressure oxidation, 1

, 25 application for patent consists in mixing an unsaturated, hydroxylated, fatty body of the kind previously described, such as castor oil, with not I 2 over %.01 a true drying oil, such as linseed oil,

or perillaoil, or the acids thereof, and subjecting 0 j the same to pressureoxidation at approximately r tof'l5 lbs. pressure by means of ordinary moist and'at a temperature of-not over 135 (3., and IpreferabIy vat about C., for approximately 10 to. ao'ihours, 'Asmau amount of aiia't'spntasfi 4 of Petrofrireagent (oil-soluble petroleumusulfqmc I a, acids) maybe Pr ent during oxidati I Ins well oil-course, that castor oilis I 4o acids containing the secondary alcoholic group, as, for example, oxidation'of lactic 'acid'lto pyro is converted intoa CO] group. The cautiousoxi- Idation of castor oil or ricinoleicacid conducted I a under the previously specified conditions results a in theyformation of aketonic acid, -which may; I

[cadence-poor! .I

2 acme-o4 age, with probably the absorption of oxygen and then conversion into hydroxyl groups, and thus the ketonic acid producedmay represent a saturated, dihydroxy acid which may be indicated by the following formula: p v

However, it is well known thatmxidatic n reactions tend to'polymerize orform ester acids,

ethers, etc., and thus the resultant product represents ketonic acids in the polymerized form,

1. e., derived from two or more molecules, at least one of which must contain a ketone group;

"ll'he formation of ketohydroxystearic acid in the usual manner (see Lewkowitsch, Chemical Technology of Oils,.Fats and Waxes", 6th edition,

volume 1, page 240) with subsequent reaction with ricinoleic acid, diricinoleic acid, ,oleicacid, triricinolein, etc., results in a compound representing substantially nothing'other than "poly keto acids. On the other hand, we are aware that the productsobtained by pressure oxidation in the manner referred'to previously, inay result in products containing a significant amount or majority of poly keto acids, but may "contain certain" other non-vketonic material of the kind presenti invarious conventional or special blown oils. Since such non-ketonic materials are also I effective quite frequently for the treatment of oil field emulsions, we prefer tov use the impure form-of poly keto acids or their salts or esters, as obtained by pressure oxidation. This ,is a matter of pure economy. The pure forms, relatively free, from extraneous materials, maybe employed.

we are fully awa e that migraa os msy take 7 place in a fatty molecule. For instance, that the formation of stearolactone from hydroxystearic acid appears to depend on the migrationof the alcoholiform hydroxyl. We are also aware that in the case ofthe common'non-fattygketonic acid, aceto-aceticacid, that certain-reactions are known to take place which suggest that acetoacetic acid may, as far as those reactions are concerned, react more as an aldehyde or" as an aldehydic acid thanas a ketonic'acid. [Such "wandering ofa hydrogen atom. and changefin positiqnof a double bond is referred to as ket o enolic tauto'rnerism (Bernthsen, 1 Text Book of Organic Chemistry. 2nd edition, 1931, page 231).; We believe" that this or a comparable change may talse place in these poly ketonic acids or bodies previously described, and possibly in regard to some reactions,'these poly ketoacids or esters thereof act more as if they were aldehydio acids or esters or saltsjthere'of. In other words, if these'polyxketonicacidbodies are to be used in a mixture where aldehydic acidsfwould be incompatible, it is also likely'that 'thesepoly ketonic acids" or their esters may be incompatible, for the reason thatth'ey really may be aldehydic acid bodies. It is to be noted that the reagents of thekind-employed for determining the presence of the carbonyl group, in ketones'also usually detect the "presence of the carbonyl group in aldehyde's. It is tobe understood that in theclaims where "the products are characterized' by the presence of ketonic radicals,- that such acids might ultimately prove to be aldehydic' acids, or at least convertible under certain con.- ditions of use, or else under certain conditions of identification, possibly they become converted into aldehydic' acids, and it is'"not intended 'that'fthe word fketonic" or "keto be-interpreted as ex--' esters.

is carried out in the following manner:

imately-4,000 lbs.'of castor oilare placed' i n a 45 cluding the meaning of "aldehydic in the sense previously described or discussed, 1. e.,- that both have the carbonyl (C0) radical present, and their ultimate composition in carbon atoms, hy-

drogen atoms, and oxy en atoms is identical. 5

Itis understood, of course, that these polymerized ketonic acids or their esters maybe converted into salts, or esters in the manner generallyemployed for the manufacture of salts or However, it should be borne in mind that saponification of, the kind which would decompose the'polymerized material into its simpler form in the same, manner that diricinolein could bedecoinposed into two molecules of ricinoleic acid, is objectionable and cannot be employed. 15 Due to the low cost of castor oil and the low "cost of the hydroxylated unsaturated materials ethanclamineas in the case of thepreferred example, which will be described subsequently. In 7 somein'stancea'it might-be desirable'to mix an alcohol, particularly a polyhydric alcohol, such 30 as glycerine or ethylene glycol; with the pressureoxidized bodies and'the'n heat'so as to, eliminate the carboxylic hydrogen. In any event, the polymeria'ed' ketonic bodies 'may be converted; into any suitable form by means of conventional re- '35 actions,'provided that the material is not decomposed so as to destroy the carbonyl radical or the polymerized state, and thus produce'simple ketonic fatty acids, 'as differentiated from poly "ketonic acid acids in the samern'ann'er as ricin- 40 olic acid-isdifferentiated from diricinoleic acid.

The manufacture of the demulsifying agent that we prefer to use in practisingour process,

Approxvessel of a convenient kind equippedwith a suitable means for heating the same to approximately 135C. and also for coolingthe heatedmass, if desired. Similarly, the vessel shouldbe equipped for maintaining pressure during oxidation at 5 (any desiredpoint, such as 45 lbs. or asmuch as '75 lbs. To this castor oil there is added approximately 400 lbs. of linseed oilo'f either the boiled type, with added-metallic driers, such as cobalt, linoleate, manganese, 'resinate, etc.,: or'the un- 55 boiled-type. Approximately 40 lbsQor lessof Pet roif agent 'are'added. The mass is then heated -up to approximately 125 C. and oxidation, by means of air, started, and-the" teinperaturev maintained during oxidation at approximately 0 C. Oxidation is carriedpnfor approximately 20 hours. At the end of the oxidation period the material will show some=free carboxylic acidity, which may be'removed by esterification with an alcohol, partioularlyapolyhydriealcohol, 65 such asglycerine or ethylene; glyco'L but we 'preafer to eliminate the acidity',,ifdesired, by the addition of an" equivalent amount of triethanolamine: The productso obtainedis ready for use in breaking on field emulsions, feith'er aloneflonin 7o suitable admixture with other reagents or'd'emulsifying agents. In many instances the most eta ffectivetreatment is obtained without theflnal neutralization with iriethanolamine. As a mat- 'ter of practical convenience, 'we 'prefcnto'dilute i cresol, anthraceneoil, etc. Alcohols particularly -'s,os5;eo4 I upon the, emulsion tobfe tr ated,j1n 'anyiortne. I

,various ways or by any ofthe venou apparatus thereage'nt with'50 by weightof asolvent composed of 'equal'volumes of solvent naphtha and methyl alcohol.

- The use of demulsifying*agents-consisting -of various sulfo-acids,-"or 'carboxy"acids, or compounds having both a sulfo group and a carboxyl group; 'is'wellknown in the treatmentof water-. I in-oilemulsions; In the use of conventional de-' I I I I I I sionofthewater ineofl type, which consistsdn 10 I mulsifying agents it is the-common practice to use them not only in the form of acids, but also in the form of salts or esters, or half salts, or

half esters, or ester salts, in case of dibasic acids.

The salts generally employed are the sodium salt, potassium salt, ammonium salt, calcium, magnesium, the triethanolamine salt, etc. The esters may be employed such as the methyl ester, ethyl ester, propyl ester, butyl ester, amyl ester, hexyl Aromatic or cyclic ester the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such'as water, petroleum hydrocarbons, such as gasoline, kerosene, stove oil, a coal tar product,

such as benzene,'-toluene, xylene, tar acid oil,

aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc. may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, f

etc. may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents.

Moreover, said material or materials may be used alone .or in admixture with other suitable well known classes of demulsifying agents, such as demulsifying agents of the modified fatty acid type, the petroleum sulfonate type, thealkylated sulfa-aromatic type, etc.

It is well known that conventionaldemulsifying' agents may be used in a water-soluble form, or

in an oil-soluble form, or-in a form exhibiting both 011 and water-solubility. Sometimes they may be used in a form which exhibits relatively limited water-solubility and relatively limited oil'- solubility.

the expression acid body is frequently-employed to mean the acid itself, or ester thereof,-:-or salt thereof. The word bodyf is'j-hereiniemg ployed in this'same sense in conformitywith its; I I g sion at the water id -oil type, which consists in prior usage in the trade, and particularlyin varibus patents of the prior art. Half salts and half esters are considered as salts, and esters, respec is brought into contact with or caused to act 1 mixed witha small amount of linseed oil.

- of the water-in oil type, which consists insubiying agent obtained by the pressure oxidation mixedwith not over 10% of linseed oil;v

' at approximately 45 lbs. pressure ofcastor oiladnow generally used to resolve or breakpetroleum emulsions with a 'chemIc aI reagent. I, M ,f {Having'Ithus described our-"invention, what e 5 claim as new anddesire to secureby Letters ate t j a V {1. A process' for'breaking a petroleumemulsubjecting the emulsion to theaction of, a de-i mulsifying agent comprising a poly keto fatty acid body.

, 2. A process for breaking a petroleum emul-i sion of the water-in-oil type, which consists in subjecting the emulsion'to the action of a demul- 15 sifying agent comprising a poly'keto fatty acid a I bodyinthei'ormoiasalt,

3. A process for breaking a petroleum emulsion oi! the water-in-oil type, which consists in suby i jeoting the'emulsion to the actionof a demulsi- 20- fying agent comprising a poly keto fatty acid body derived at least in partfrom castoroil. 4. Aprocess for breaking a petroleum emulsion ofv the water-in-oil type, which consists in sub- 4 I jeeting the emulsion to the action .of a dem'ulsi- 25 tying agent comprising a poly ,keto fatty acid body in the form. of a salt,-derived'at least in part from castor oil. Y v 7 5. A'process for breaking a petroleum emul- I sion of the water-in-oil type, which consists in 30;

subjectingthe emulsion to the action of a demulsifying agent comprising a poly keto fatty of thewater-in-oil type, which consists in sub-' .iecting the emulsion to the action of a demulsi- -i'ying agent comprising a poly keto fatty acid body in the form of a salt, derivedby pressure I oxidation of castor oil at a relatively low tem 40 I perature.

'l. A process for breaking a petroleum emulsion of the 'water in-oil type, which consists in sub- .iecting the emulsion-to the action of a demulsi- I r fying agent obtained by the pressure oxidation 45 at relatively low temperature of castor oiladmixed with a small amount of a true dryingoil.

8. A process for breaking a petroleum emulsion I of the water-in-oil type, which consists in sub jecting the emulsion to the action of a. demulsi- 50.

9. A process for breaking a petroleum emulsion jectingthe emulsion to the actioneof a demulsia at relatively low temperature of castor oil ad-- 10. A process for breakinga petroleum emulsion of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent obtained by pressure oxidation mixed'with not over 10% oflinsecd oil and said oxidation being conducted atatemperature-.0! app oxima e y-C.

11; A: process-:ior a petroleum emu] subjecting'the emulsion to the-action of a demul- 70 sifying agent obtainedby pressure oxidation at approximately 45 lbs. pressure of castor oil ad mixed with not, over 10% of linseed oil and said e4 r V 1.9 m rtion of the earbonlic hydrogen present by means uttrlethnnolamin'ef W I 12. A p1 oces s 1017 breaking a betroleurnjemnl slon 01' the waten-in-ofl type, whieh consistsnin subjectingthe emulsion tq thenctibrl of a. demuldrying agent bt'ained by pressure oxidation at approximately '45 lbs. presu'rebf cnsto'r ofl admixed with not over 10% 0t linseedoil an'd sa id K oxidation being conducted fat 2. tempernture of mvmgnidnoaiwf; BERNHARD KEISER. m'rnugmwm'mn. 

